Benzoxanthene and benzothioxanthene

ABSTRACT

IN WHICH X represents an oxygen or sulfur atom, Y represents an oxygen atom or a   Valuable benzoxanthene and benzothioxanthene dyestuffs of the general formula

United States Patent 1 Troster 1 Sept. 18, 1973 BENZOXANTHENE AND BENZOTHIOXANTHENE Helmut Troster, Frankfurt am Main, Germany Farbwerke Hoechst Aktiengesellschaft Vormals Meister Lucius & Bruning, Frankfurt am Main, Germany Filed: Apr. 12, 1971 Appl. No.: 133,351

[75] inventor:

[73] Assignee:

' Foreign Application Priority Data Apr. I4, 1970 Germany P 20 17 764.4

[52] US. Cl 260/328, 260/335, 260/281,

252/3012 R, 8/4 [51] Int. Cl. C07d 7/42, C07d 65/16 References Cited UNITED STATES PATENTS 2/1968 Fuchs et al. 260/328 x 4/1935 May zen/345.2 x

Primary Examiner-John M. Ford Attorney-Curtis, Morris & Safford [57] ABSTRACT Valuable benzoxanthene and benzothioxanthene dye- Field of Search 260/3452, 335, 328 I stuffs of the general formula in which X represents an oxygen or sulfur atom, Y represents an oxygen atom or a 4 Claims, No Drawings BENZOXANTHENE AND BENZOTHIOXANTHENE The present invention relates to new valuable benzoxanthene and benzothioxanthene dyestuffs of the general formula V V 5 in which X represents an oxygen or sulfur atom, Y represents an oxygen atom or a dicarboxylic acid derivatives of the general formula in which X, Y, R, and R have the meanings given above, are sulfonated.

The sulfonation may be effected, for example, by treating the compound of formula (2) with concentrated or fuming sulfuric acid at room temperature or at an elevated temperature, the degree of sulfonation being determined by the temperature used, the concentration of the sulfuric acid used and by the reaction time. It is suitable to effect the sulfonation at temperatures in range of from about C toabout 170 C using a 95 percent or fuming sulfuric acid having a SO content of up to about 20 percent.

The anhydrides or imides of formula 2 used as starting compounds may be obtained according to the process described in German Patent 1 297 259 and French Patent Specification l 590 506. by heating in the presenceof copper or copper salts the diazonium salts of compounds of thelormula in which X, Y, R, and R have the meanings given above, Z, represents a hydrogen atom and Z represents an amino group, or Z, represents an amino group and Z represents a hydrogen atom.

The dyestuffs of the present invention are excellently suited as fluorescing dyestuffs in the dyeing of condensation resins to which they impart luminous greenish yellow to orange yellow shades. The dyeings produced with these dyestuffs are distinguished by excellent fastness to bleeding and good to very good fastness to light. In addition, they are also suitable for the-dyeing and printing of plastic materials, for example of polyamides.

The following Examples illustrate the invention:

EXAMPLE 1 28.8 g of benzoxanthene-3,4-dicarboxylic acid anhydride were introduced portionwise into 120 g of fuming sulfuric acid (20% S0,, content). The temperature of the reaction mixture thereby rose to C. The temperature was then raised within 30 minutes to C and maintained for 30 minutes. After cooling, the sulfonation mixture was poured onto g of ice. After a short time, the luminous yellow sulfonation product of the formula EXAMPLE 2 The sulfonation according to Example l was repeated, with the exception that the sulfonation mixture was stirred for 6 hours at l25l30 C. The dyestuff of the formula which was isolated in the same manner corresponded with regard to tinctorial behavior largely to that of the afore-mentioned product.

EXAMPLE 3 which dissolved in water gave an intensively green fluorescent solution.

manner described in Example 1 into 120 g of fuming 5 EXAMPLE 5 sulfurlc acid S0 content) and the whole was Stirred for 3 hours at 0 0 0 After the usual 40.7 g of benzoth1oxanthene-3,4-d1carboxyl1c ac1dworking up, there was obtained the dyestuff of the for- Nz)4"dlmethylphenyhmlde were mtroduced m mula portlons at C into 120 g of 20% oleum and the H whole was then stirred for 3 hours at C.

| 10 ml of water were then added dropwise at room temperature and the orange sulfonic acid of the formula NNH1 O (s01H)1 CHaO 1 CH: It was found to dye condensation resins, for example toluene-sulfonamide-urea-formaldehyde resins, lumi- CH3 a )z nous greenish yellow shades having very good fastness 20 properties.

EXAMPLE 4 i \S A mixture of 15.0 g of 9-methylbenzoxanthene-3,4- dicarboxylic acid-N-2, 4'-dimethylphenylimide and 25 D i sulflurlc 19 were for'z L i was isolated in known manner. It was crystallized from t g f mg t ere was 0 tame t e a mixture of glacial acetic acid and concentrated hyyes u 9mm? 7 gdrochloric acid in the form of orange-colored small 0 CH, 30 ineedles which were found to dissolve in water to give an intensively yellow green fluorescence solution. Condensation resins could be dyed with this dyestuff lumi (SOSH)I nous orange-yellow shades which showed good fastness 0 to light and very good fastness to bleeding.

The following Table shows other yellow green to orange yellow dyestuffs which can be obtained according 0 v "to the methods described in the Examples.

Y )=o-(s 0311),, R

X Sulful nation 's according to X Y Rl R: R; 11 Example Example:

li'kiinu'n i NOCII1 N((JlI:)10- II N(CII' ):OCHa

NCl[a 'luhlc ontinucd nation according to X Y R1 R: R; 11 Example Example 10 s 0 CH3 cm 11 1.3 1

17 s 3 11 11 11 z s z 1s s H 01 1-1 2 2 5 N- -Cl 20 s II 11 11 1.6 3

We claim: ,3. A dyestuff of the formula 1. A dyestuff of the formula I 7 v VA ,A V O i 0 l I 0 R1 0 s.o,H).. l

5 011 o i 3 a -(S0a )1.0 x l 0 .i

wherein X i5 oxygen or sulfur, R, ancl R each is hydro- 4O 4. A dyestuff of the formula gen, chlorine, bromine, lower alkyl or lower alkoxy and n is a value of from 1 to 3. 0

2. a dyestuff of the formula )I\ O O )K m =0 0 i i a )1.s O J -J( a )1.4 50 0 t 1 e t t 

2. a dyestuff of the formula
 3. A dyestuff of the formula
 4. A dyestuff of the formula 